Multicompartment polymeric colloids from functional precursor Microgel: Synthesis in continuous process.

Raspberry-like poly(oligoethylene methacrylate-b-N-vinylcaprolactam)/polystyrene (POEGMA-b-PVCL/PS) patchy particles (PPs) and complex colloidal particle clusters (CCPCs) were fabricated in two-, and one-step (cascade) flow process. Surfactant-free, photo-initiated reversible addition-fragmentation transfer (RAFT) precipitation polymerization (Photo-RPP) was used to develop internally cross-linked POEGMA-b-PVCL microgels with narrow size distribution. Resulting microgel particles were then used to stabilize styrene seed droplets in water, producing raspberry-like PPs. In the cascade process, different hydrophobicity between microgel and PS induced the self-assembly of the first formed raspberry particles that then polymerized continuously in a Pickering emulsion to form the CCPCs. The internal structure as well as the surface morphology of PPs and CCPCs were studied as a function of polymerization conditions such as flow rate/retention time (Rt), temperature and the amount of used cross-linker. By performing Photo-RPP in tubular flow reactor we were able to gained advantages over heat dissipation and homogeneous light distribution in relation to thermally-, and photo-initiated bulk polymerizations. Tubular reactor also enabled detailed studies over morphological evolution of formed particles as a function of flow rate/Rt.

Amphiphilic PVCL/TBCHA microgels: From synthesis to characterization in a highly selective solvent.

Thermoresponsive copolymer microgels based on the biocompatible monomer N-vinylcaprolactam (VCL) and the hydrophobic comonomer 4-tert-butylcyclohexylacrylate (TBCHA) with highly tunable comonomers ratio were for the first time synthesized by miniemulsion polymerization. Their physical properties in aqueous solution and at the solid interface were characterized using dynamic light scattering (DLS), atomic force microscopy (AFM) and dissipative particle dynamics (DPD) simulations. The results show a significant decrease of the swelling rate of the obtained microgels with an increase of the amount of the hydrophobic comonomer. In the case when the fraction of TBCHA is equal or higher than the fraction of VCL, the microgels become almost insensitive to the temperature changes, and the amount of water inside the microgels appeared to be diminishingly small. In the opposite case, if the VCL fraction is major, the copolymer microgels preserve their softness and deformability while being adsorbed onto a solid surface. At the same time, all samples have shown a good colloidal stability and a low polydispersity in size. Thus, the presented polymerization technique is applicable for the fabrication of microgels using hydrophobic monomers, which are not accessible by conventional precipitation polymerization. We demonstrate that the mechanical properties and the temperature-responsiveness of the copolymer microgels can be precisely adjusted by the content of the hydrophobic comonomer.